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Published November 1951 | public
Journal Article

Small-Ring Compounds. VIII. Some Nucleophilic Displacement Reactions of Cyclopropyl, Cyclobutyl, Cyclopentyl and Cyclohexyl p-Toluenesulfonates and Halides

Abstract

A study has been made of the rates and products of some nucleophilic displacement reactions of cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl p-toluenesulfonates and halides. The solvolysis reactivity sequence of the p-toluenesulfonate's in dry acetic acid was found to be cyclopentyl ~ cyclobutyl > cyclohexyl >> cyclopropyl. The hydrolysis rate sequence for the corresponding chlorides in 50% ethanol-50% water solution was similar except that the cyclobutyl derivative was more reactive than the cyclopentyl derivative. In acetolysis and hydrolysis, the cyclopropyl and cyclobutyl compounds react with rearrangement but without elimination. The cyclopentyl and cyclohexyl derivatives give no detectable rearrangement products but do yield considerable cyclopentene and cyclohexene, respectively. The reactivity sequence of the bromides toward sodium iodide in acetone was found to be cyclopentyl > cyclobutyl > cyclohexyl >>cyclopropyl. The significance of the experimental results lies primarily in the lack of any simple correlation of reactivity with ring size in contrast to expectations based on other properties of small-ring compounds.

Additional Information

© 1951 American Chemical Society. Received February 23, 1951. National Research Fellow in Chemistry, Harvard University, 1946-1948.

Additional details

Created:
August 19, 2023
Modified:
October 25, 2023